CN87101910A - 含少量磷或不含磷润滑组合物的氨基甲酸酯添加剂 - Google Patents

含少量磷或不含磷润滑组合物的氨基甲酸酯添加剂 Download PDF

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CN87101910A
CN87101910A CN87101910.8A CN87101910A CN87101910A CN 87101910 A CN87101910 A CN 87101910A CN 87101910 A CN87101910 A CN 87101910A CN 87101910 A CN87101910 A CN 87101910A
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CN1009560B (zh
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比特希·简·布特克
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Lubrizol Corp
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Abstract

通过与具有下式(I)的添加剂(其中，R1、R2、R3、R4、X、Z及a的定义请见说明书)配制在一起而提供了一种含少量磷或不含磷的润滑组合物：
这些添加剂改善了润滑组合物的极压性质和抗磨性质。

Description

本发明涉及到多种用于润滑组合物的氨基甲酸酯添加剂。更具体地说，本发明涉及到多种氨基甲酸酯添加剂，这些是由胺与二硫化碳及含有活性不饱和双键或α-氯或α-溴羧酸或其衍生物的反应物反应而得到的。这些添加剂改善了润滑组合物，特别是不含磷或含少量磷的润滑组合物的极压和抗磨性质。
在本技术领域中已经知道，由含有活性不饱和双键的反应物衍生出的氨基甲酸酯化合物具有许多不同的用途。例如，美国专利No.2，067，494公开了多种用于加速橡胶硫化的二硫代氨基甲酸酯。
美国专利No.2，710，872公开了在医药、杀菌剂、杀虫剂和猪油抗氧化剂的生产中用作中间体的二硫代氨基甲酸及其酯。
美国专利No.2，841，530公开了多种二硫代氨基甲酸盐，这些盐用于配制使头发卷曲的组合物。
美国专利No.2，897，152公开了含有某类能够改善油的极压性质的二硫代氨基甲酸酯添加剂的汽轮机油。
美国专利No.3，211，771公开了用于杀虫剂组合物中的二硫代氨基甲酸2-氰基乙烯酯。
美国专利No.3，890，363和3，833，496公开了在润滑油和润滑脂中用作抗氧化剂和抗磨添加剂的某类二硫代氨基甲酸酯化合物。
美国专利No.4，130，578公开了各种二硫代苯氨基甲酸（烷氧羰基）烷基酯，这些酯可作为治疗器官移植的排异反应和其它免疫疾病的免疫调节剂。
美国专利No.4，064，265公开了可用作驱肠虫剂的二硫代氨基甲酸。
美国专利No.4，254，142公开了可作为免疫抑制剂的降冰片硫基-和二硫代苯氨基甲酸。
美国专利No.4，161，534公开了可作为驱肠虫剂的苯氧苯基或苯氨苯基取代的二硫代氨基甲酸酯。
美国专利No.4，202，832公开了可作为降脂剂（lipid-lowering    agents）的各种硫代氨基甲酰硫基脂肪酸衍生物。
但是，所有上述公开的内容中都没有提及可作为润滑组合物添加剂的本发明的这一类氨基甲酸酯添加剂。
本发明提供了含有某类氨基甲酸酯添加剂的含少量磷或不含磷的润滑组合物。本发明的氨基甲酸酯添加剂改善了润滑组合物的极压性质和抗磨性质。
此外，本发明还提供了含有本发明的氨基甲酸酯添加剂的润滑组合物，其中包括自动传动液、液压液和润滑脂，及这些润滑组合物的浓缩物。
本发明进一步提供了在润滑组合物中可作为极压添加剂和抗磨添加剂的氨基甲酸酯化合物的有效制备方法。
通过阅读并理解本说明书，本技术领域的技术人员能够弄清楚本发明的这些目的和其它目的。
在润滑组合物和润滑脂中通常加入添加剂以改善其性质。过去，将一些添加剂（如二烷基二硫代磷酸锌）与润滑油和润滑脂组合物配制在一起以改善其抗磨和抗氧化性质。在某些润滑油或润滑脂中还可加入一些其它化学制品或添加剂以影响其其它性质，例如，加入聚丁烯基琥珀酸及其衍生物以改善润滑油的分散性。尽管二烷基二硫代磷酸锌是非常有效的抗磨剂和抗氧化剂，但在工业上需要特殊配制的不含磷或只含少量磷的润滑油和润滑脂。
本发明的发明人发现，某类氨基甲酸酯化合物可有效地改善润滑油和润滑脂组合物的极压性质和抗磨性质，而这些润滑油和润滑脂组合物不含磷或含少量磷。
可用下式来说明本发明的氨基甲酸酯添加剂：
Figure 87101910_IMG25
其中，R1和R2独立地代表含有1至大约7个碳原子的烷基、芳基、芳烷基或二者一起形成一个脂环基或通过氮原子一起形成杂环基;X为O或S;a为1或2;R3和R4独立地代表H、烷基或芳基;Z代表CN、
Figure 87101910_IMG26
、
Figure 87101910_IMG27
（其中R5为氢、烷基或芳烷基）、
Figure 87101910_IMG28
，其中Y为H、OH、R6（其中R6为烷基、芳基或芳烷基）、OR6、OR7-OH（其中R7为含1至大约7个碳原子的亚烷基）和NR8R9（其中R8和R9独立地代表氢、烷基、脂环基、杂环基或一起形成一个脂环基或通过氮原子一起形成杂环基，但a须为1，Y不是OR6）。
在本发明的范围内一组优选的化合物是由上式定义的，且其中X为 S，R3和R4独立地代表H或烷基、a为2，Z为
Figure 87101910_IMG29
[其中Y为OH、R6、OR6、OR7-OH（R7为1至大约7个碳原子的亚烷基）或NR8R9]的化合物。
一组最优选的化合物是由上式定义的，且其中X为S、R3和R4为H或甲基、Y为OH、OR6（R6为甲基或乙基）、OR7-OH（R7为1至大约4个碳原子的亚烷基）或NR8R9（R8和R9为H）。
使用上述氨基甲酸酯类化合物的一个优点是这些酯可以通过一步反应高产率地制备。这些化合物是从胺、二硫化碳或氧硫化碳或者由产生这些反应物的原料和含有活性不饱和双键或α-氯或α-溴羧酸或其衍生物的反应物得到的。将这些反应物加到反应器中并搅拌，无需加热，因为该反应是放热的。一旦反应达到温升温度，将反应混合物保持在温升温度范围内的某一温度以保证反应完全，随后在减压下除去挥发性组分。然后，将混合物过滤并得到高产率的最终产物。
关于可用于制备本发明化合物的不同反应物，已经指出可以使用二硫化碳（CS2）、氧硫化碳（COS）或产生这些反应物的原料。
关于反应物胺，可以使用含有1至大约7个碳原子的烷基、芳基、芳烷基或由胺上的氮原子成环的杂环基的仲胺。已经发现，可用于本发明中的具体的胺包括：二甲胺、二乙胺、二丙胺、二丁胺、二戊胺、二己胺和二庚胺。此外，还有二苯胺、二苄胺等。可用于本发明中的胺还有不对称胺如N-甲基乙胺、N-乙基丁胺、N-乙基戊胺等。类似地，还可以使用N-戊基苯胺等。
适宜的杂环化合物为氮丙啶、氮杂环丁烷类、吡咯烷类、吡咯烷、吡啶、二氢吡啶和四氢吡啶、吡咯、吲哚、喹啉、吗啉、甲基吡啶、哌啶等。也可以使用这些杂环胺的两种或两种以上的混合物。典型的杂环胺为饱和的5-和6-员杂环胺。
关于含有活性不饱和双键或α-氯或α-溴羧酸的反应物，可用下式来表示：
其中，R10和R11独立地代表H、烷基、芳基、Cl或Br;R′为H、烷基、芳基或芳烷基;X为0或1，b为0或1（x+b为1）;R′ 3为H、烷基或芳基、氯或溴;Z为CN、
Figure 87101910_IMG30
Figure 87101910_IMG31
Figure 87101910_IMG32
（其中R5为H、烷基或芳烷基）、
Figure 87101910_IMG33
，其中Y为H、OH、R6（R6为烷基、芳基或芳烷基）、OR6、OR7-OH（R7为1至大约7个碳原子的亚烷基）、NR8R9（其中R8和R9独立地代表H、烷基、脂环基、杂环基或二者一起形成脂环基或通过氮原子一起形成杂环基，但X须为0，Y不能为OR6）。
作为上述式（Ⅱ）的具体实例，可以列举的有：丙烯酸甲酯、丙烯酸乙酯、丙烯酸2-乙基己酯、丙烯酸2-羟基乙酯、甲基丙烯酸乙酯、甲基丙烯酸2-羟基乙酯、甲基丙烯酸2-羟基丙酯、丙烯酸2-羟基丙酯、丙烯酰胺、丙烯腈、乙磺酰基乙烯、甲基亚磺酰基乙烯等。此外，可用α-氯乙酸和α-溴乙酸及它们的衍生物来制备本发明的化合物。
以上讨论的用来制备本发明的氨基甲酸酯化合物所用反应物的相对量不是很严格的。反应器的进料比可在较宽的范围内变动，经济效益和所需产物的量是控制因素。因此，胺与CS2或COS反应物及与含不饱和双键的反应物的进料比可在5∶1∶1到1∶5∶1到1∶1∶5的范围内变动。作为最佳实施方案，这些反应物的进料比是1∶1∶1。
在下面的实施例中，进一步说明了本发明具体化合物的制备方法。这些实施例是为了使本领域的技术人员了解如何在本发明的范围内操作，而不对本发明的范围起限制作用，本发明的范围在权利要求中所定义。需要指出的是，在下述实施例及整个说明书和权利要求书中，除非另有说明，所有的百分数和份数均以重量计。
实施例1
在一个1升的4-颈烧瓶上装上机械搅拌器、温度计、加料漏斗和一个水冷回流冷凝器。加入116克丙烯酸2-羟基乙酯和76克二硫化碳。用3.1小时加入129克二丁胺，反应放热至47℃。将混合物搅拌2小时。在45-55℃连续加热并保持该温度2.5小时。冷却混合物。于68℃及9毫米汞柱下真空汽提混合物。没有收集到馏出液。将反应混合物在硅藻土上过滤。产量为303克透明的黄色液体。
实施例2
在一个1升的烧瓶上装上机械搅拌器、温度计、加料漏斗和一个水冷回流冷凝器。向该烧瓶中加入71克丙烯酰胺和60克95%的乙醇。将混合物在室温下搅拌45分钟。再加入40克95%的乙醇以完全溶解丙烯酰胺。向该溶液中加入76克二硫化碳。在1.23小时内加入157克二戊胺。反应放热至41℃。在50-55℃加热该混合物并保持在该温度3小时。随后将该混合物在91℃和20毫米汞柱下真空汽提，得到113克馏出液。将残余物在硅藻土 过滤器上过滤，收集滤液得到281克透明的黄色粘滞液体。根据理论产量为304克计算，产率为92.4%。
实施例3
在一个1升的烧瓶上装上机械搅拌器、温度计、加料漏斗和一个干冰/异丙醇冷凝器。向烧瓶中加入157克二戊胺。在搅拌下加入76克二硫化碳。在加入二硫化碳后大约50分钟内，反应放热至大约55℃。向烧瓶加入50克甲苯，然后于25℃下在45分钟内加入56克丙烯醛。加入丙烯醛后反应放热至45℃。在6小时内搅拌混合物并冷却至室温。在50℃下再将该混合物搅拌4.5小时，静置过夜。在85℃及8毫米汞柱下真空汽提该混合物，得到64克馏出液。将残余物在硅藻土过滤器上过滤，得到240克滤液，为一透明的红色粘稠液体。根据理论值为289克计算，产率为83%。
实施例4
在一个1升的烧瓶上装上一个机械搅拌器、温度计、加料漏斗和一个水冷回流冷凝器。向烧瓶中加入172克丙烯酸甲酯和156克二硫化碳。在室温下搅拌该混合物，用2.75小时加入146克二乙胺，放热使温度升至62℃。然后将该混合物于55℃保持2.5小时，随后静置过夜使其冷却。将该反应混合物搅拌并加热至大约55℃，在该温度下保持2小时。在73℃及9毫米汞柱下真空汽提该混合物。将残余物在硅藻土过滤器上过滤，收集到447克透明的棕色滤液。根据理论值为470克计算，产率为95.1%。
实施例5
在一个1升的烧瓶中装上一个机械搅拌器、温度计、加料漏斗和一个水冷回流冷凝器。向烧瓶中加入86克丙烯酸甲酯和76克二硫化碳。在室温下搅拌该混合物，在2.17小时内加入129克二乙胺，反应放热至53℃。然后加热反应混合物并在55℃保持4小时。在76℃及8毫米汞柱下真空汽提该混合物。将残余物在硅藻土过滤器上过滤，得到274克透明的黄色滤液。
实施例6
在一个1升的烧瓶上装上机械搅拌器、温度计、加料漏斗和一个水冷回流冷凝器。向烧瓶中加入116克丙烯酸2-羟基乙酯和76克二硫化碳。在室温下搅拌该混合物，并在1.3小时内加入157克二戊胺。反应放热至68℃。将混合物冷却45分钟并静置过夜。用2小时将混合物搅拌并加热至大约60-65℃。在98℃及10毫米汞柱下真空汽提该混合物，得到微量的馏出液。在10克硅藻土上过滤残余物，得到332克透明的黄色滤液。
已经发现，上述实施例中说明的本发明的化合物在含少量磷或不含磷的润滑组合物的制备中可用作极压添加剂和抗磨添加剂。本发明的化合物还可作为其它功能流体（functional    fluids）的添加剂，这些功能流体包括自动传动液和液压液。
可以通过下述方法将本发明的氨基甲酸酯化合物与润滑油或自动传动液等配制在一起，即直接将化合物与具体要配制的油或功能流体混合在一起。也可以将润滑油或其它功能流体与本发明化合物的浓缩液一起配制。这种浓缩液的配制，是将1%至大约99%（重量）的至少一种本发明的氨基甲酸酯化合物加到基本上惰性的、通常为液态的有机稀释剂或溶剂（如苯、甲苯、二甲苯、石脑油、矿物油、乙二醇单甲醚等）中。
与具体润滑剂配制在一起的氨基甲酸酯添加剂的量可在较宽的范围内变动，但这个量必须能够有效地改善润滑剂的极压性质和抗磨性质。较好的添加剂用量为需配制的润滑剂的0.01%至大约10%（重量）。在最佳实施方案中，该量可在需配制的润滑剂的大约0.1%至大约5%（重量）的范围内。
本发明的与某种功能流体配制的组合物还可含有其它添加剂和化学制品如分散剂、抗氧化剂等。这样的其它添加剂和化学制品的实例包括：成灰或无灰型的清净剂和分散剂、抗腐蚀和抗氧化剂、倾点降低剂、助极压剂、色泽稳定剂和防泡剂。在美国专利No.3，541，012、美国专利No.3，697，428和美国专利No.4，234，435中详细地描述并公开了这些其它添加剂和化学制品。将这些涉及到其它添加剂的专利引用在这里以作参考。
根据本发明，较好的分散剂为至少一取代的琥珀酸或其衍生物，其中的取代基是从聚烯烃衍生的，该聚烯烃的特征在于 Mn值为500至大约10，000且 Mw/ Mn值为1.0至大约4.0。
还发现，本发明的添加剂化合物可用于配制各种润滑脂组合物中。本发明的氨基甲酸酯添加剂可用于天然的和合成的润滑油和润滑脂中。合成的油包括聚烯烃油（例如聚丁烯油、癸烯低聚物等）、合成酯（例如癸二酸二壬酯、三羟甲基丙烷的三辛酸酯等）、聚乙二醇油等。通过向这些油中加入增稠剂（如脂肪酸，例如硬脂酸，的钠、钙、锂或铝盐）来制备润滑脂。本发明的油和润滑脂是通过将一定量的本发明氨基甲酸酯添加剂与油或润滑脂混合而制备的，氨基甲酸酯的加入量应足以改善润滑油和润滑脂的极压性质和抗磨性质。可取的浓度范围为0.1%至大约5%（重量）。
为进一步说明各种含有本发明组合物的功能流体组合物，特别是润滑组合物，给出下面的说明例。需要再次指出的是，下述例子仅起说明作用，并不对本发明的范围构成任何限制，而本发明的范围仅在权利要求中加以定义。所有的份数和百分比均以重量计。
典型的本发明的组合物列于下表。
表Ⅰ
组份    A    B    C    D    E    F
基础油    90.37    90.87    92.82    95    81.13    83.18
实施例4的产物    2.00
实施例5的产物    0.11    0.11    3.86    2.50
实施例6的产物    2.60
聚丁烯基琥珀酸
酐与乙烯多胺的
反应产物    3.61    2.50
聚丁烯基琥珀酸
酐与乙烯多胺及
季戊四醇的反应
产物    2.50
聚丁烯基琥珀酸
酐与乙烯多胺及
二硫化碳的反应
产物    2.00    2.00
聚丁烯基琥珀酸
酐与乙烯多胺及
硼酸的反应产物    1.00    1.00
碱性烷基苯磺酸钙    1.79    1.79    1.10
碱性烷基苯磺酸镁    1.35    0.65
表Ⅰ（续）
组份    A    B    C    D    E    F
马来酸酐-苯乙烯
共聚物与醇及胺的
反应产物    3.50    3.50    1.11    0.20
氢化苯乙烯-二烯
烃嵌段共聚物粘度
改进剂    9.00
乙烯-丙烯共聚物
粘度改进剂    7.00
硫化脂    0.50
有机硫化合物与环
氧化物的反应产物    0.50    0.50
硫化烯烃    2.50    1.50
二巯基噻二唑的酯    0.17    0.10    0.06
硫化狄尔斯-阿德
耳加成物    0.60
油溶性含磷极压添
加剂    1.47
烷基化芳基胺    0.10    0.10    0.50    0.30
乙氧基化脂肪胺    0.09    0.09
脂肪族酰胺    0.11    0.10
脂肪族胺    0.39
硅氧烷防泡剂    0.042    0.042    0.066    0.006    0.006
对在表Ⅰ中描述的完全配制好的润滑组合物中所含的各实施例的产物进行泰姆肯“OK”负荷试验及接触压力试验，实验是根据美国材料试验标准D2782的方法进行的，所不同的是在“OK”负荷试验中，在试验程序上有下列不同：
1.仅用试验润滑剂“湿润”试验杯和模块表面（在模块表面上大约滴5滴）。在试验过程中没有试样在表面上循环。
2.试验在负荷下进行5分钟。
3.这个程序称作“OK”负荷试验，以确定美国材料试验标准D2782所述的“OK”负荷，所不同的是采用下述负荷增量：
a.“OK”负荷≤20磅：确定“OK”负荷为最窄的1磅。
b.“OK”负荷＞20磅：采用美国材料实验标准D2782所描述的标准负荷增量以确定“OK”负荷。
表Ⅱ
各种氨基甲酸酯的泰姆肯值
实施例    %（重量）    OK负荷（磅）    接触压力（磅/
平方英寸）
无添加剂    12    5，783
2    1    15    8，450
4    2    17    7，850
5    2    25    11，025
5    1    17    6，900
6    2    20    10，150
6    1    20    7，800
虽然通过某些较佳的实施方案已对本发明作了描述和说明，但本技术领域的技术人员将会意识到，在不超出本发明的精神实质的情况下，可对本发明进行各种改善、改进和替代。例如，浓度可以不同于上面给出的较佳范围，从而得到各种油基润滑油料或发动机型等的油料。因此仅由下述权利要求的范围来限定本发明。

Claims (18)

1、一种含少量磷或不含磷的润滑组合物，该组合物含有较大量的粘性润滑油和较少量的下式(Ⅰ)所定义的添加剂：
其中，R1和R2独立地代表含1至大约7个碳原子的烷基、芳基、芳烷基或二者一起形成一个脂环基或通过氮原子一起形成杂环基，X为O或S，a为1或2，R3和R4独立地代表H、烷基或芳基，Z为CN、 、
Figure 87101910_IMG4
(其中R5为氢、烷基或芳烷基)、
Figure 87101910_IMG5
，其中Y为H、OH、R6(其中R6为烷基、芳基或芳烷基)、OR6、OR7-OH(其中R7为含1至大约7个碳原子的亚烷基)、NR8R9(其中R8和R9独立地代表氢、烷基、脂环基、杂环基或二者一起形成一个脂环基或通过氮原子一起形成杂环基，但a须为1，Y不是OR6)。
2、根据权利要求1的润滑油，其中X为S，R3和R4独立地代表氢或烷基，a为2，Z为
Figure 87101910_IMG6
，其中Y为OH、R6、OR6、OR7-OH（其中R7为含1至大约7个碳原子的亚烷基）或NR8R9。
3、根据权利要求2的润滑油，其中R3和R4独立地代表氢或甲基，Y为OH、OR6（其中R6为甲基或乙基）、OR7-OH（其中R7为含1至大约4个碳原子的亚烷基）或NR8R9（其中R8和R9为氢）。
4、用于配制润滑组合物的浓缩液，该浓缩液含有通常为液态的基本上是惰性的有机溶剂/稀释剂和大约1%至大约99%（重量）的权利要求1所述的添加剂。
5、用于配制润滑组合物的浓缩液，该浓缩液含有通常为液态的基本上是惰性的有机溶剂/稀释剂和大约1%至大约99%（重量）的权利要求3所述的添加剂。
6、根据权利要求1的润滑油组合物，其中还含有分散剂。
7、根据权利要求6的润滑油，其中所述的分散剂为至少一取代的琥珀酸或其衍生物，其中的取代基是从聚烯烃衍生的，该聚烯烃的特征在于 Mn值为500至大约10，000且 Mw/ Mn值为1.0至大约4.0。
8、一种改善含少量磷或不含磷的粘性润滑油的极压性质的方法，该方法包括向该润滑油中混入少量的至少一种下式所示的添加剂：
Figure 87101910_IMG7
其中，R1和R2独立地代表含1至大约7个碳原子的烷基、芳基、芳烷基或二者一起形成一个脂环基或通过氮原子一起形成杂环基，X为O或S，a为1或2，R3和R4独立地代表H、烷基或芳基，Z为CN、
Figure 87101910_IMG8
、
Figure 87101910_IMG9
（其中R5为氢、烷基或芳烷基）、
Figure 87101910_IMG10
，其中Y为H、OH、R6（其中R6为烷基、芳基或芳烷基）、OR6、OR7-OH（其中R7为含1至大约7个碳原子的亚烷基）、NR8R9（其中R8和R9独立地代表氢、烷基、脂环基、杂环基或二者一起形成一个脂环基或通过氮原子一起形成杂环基，但a须为1，Y不是OR6）。
9、根据权利要求8的润滑油，其中X为S，R3和R4独立地代表氢或烷基，a为2，Z为
Figure 87101910_IMG11
，其中Y为OH、R6、OR6、OR7-OH（其中R7为含1至大约7个碳原子的亚烷基）或NR8R9。
10、根据权利要求9的润滑油，其中R3和R4独立地代表氢或甲基，Y为OH、OR6（其中R6为甲基或乙基）、OR7-OH（其中R7为含1至大约4个碳原子的亚烷基）或NR8R9（其中R8和R9为氢）。
11、一种用于制备含少量磷或不含磷的润滑油、润滑脂或自动传动液的添加剂，该添加剂由下式定义：
其中，R1和R2独立地代表含1至大约7个碳原子的烷基、芳基、芳烷基或二者一起形成一个脂环基或通过氮原子一起形成杂环基，X为O或S，a为1或2，R3和R4独立地代表H、烷基或芳基，Z为CN、
Figure 87101910_IMG13
、
Figure 87101910_IMG14
（其中R5为氢、烷基或芳烷基）、
Figure 87101910_IMG15
，其中Y为H、OH、R6（其中R6为烷基、芳基或芳烷基）、OR6、OR7-OH（其中R7为含1至大约7个碳原子的亚烷基）、NR8R9（其中R8和R9独立地代表氢、烷基、脂环基、杂环基或二者一起形成一个脂环基或通过氮原子一起形成杂环基，但a须为1，Y不是OR6）。
12、根据权利要求11的润滑油，其中X为S，R3和R4独立地代表氢或烷基，a为2，Z为
Figure 87101910_IMG16
，其中Y为OH、R6、OR6、OR7-OH（其中R7为含1至大约7个碳原子的亚烷基）或NR8R9。
13、根据权利要求12的润滑油，其中R3和R4独立地代表氢或甲基，Y为OH、OR6（其中R6为甲基或乙基）、OR7-OH（其中R7为含1至大约4个碳原子的亚烷基）或NR8R9（其中R8和R9为氢）。
14、一种含少量磷或不含磷的润滑组合物，该组合物含有较大量的粘性润滑油和较少量的添加剂，该添加剂是从含有下述组份的反应物中衍生出来的：
（A）二硫化碳、氧硫化碳或产生它们的原料，
（B）具有式R′R″NH的胺，其中R′和R″相同或不同，为1至大约7个碳原子的烷基、芳基或芳烷基，或二者一起形成脂环基或通过氮原子一起形成杂环基，
（C）具有下式的反应物：
其中，R10和R11独立地代表H、烷基、芳基、Cl或Br;R′为H、烷基、芳基或芳烷基;X为0或1，b为0或1（x+b为1）;R′ 3为H、烷基或芳基、氯或溴;Z为CN、
Figure 87101910_IMG17
、
Figure 87101910_IMG18
Figure 87101910_IMG19
（其中R5为H、烷基或芳烷基）、
Figure 87101910_IMG20
，其中Y为H、OH、R6（R6为烷基、芳基或芳烷基）、OR6、OR7-OH（R7为1至大约7个碳原子的亚烷基）、NR8R9（其中R8和R9独立地代表H、烷基、脂环基、杂环基或二者一起形成脂环基或通过氮原子一起形成杂环基，但X须为0，Y不能为OR6）。
15、一种用于制备含少量磷或不含磷的润滑油、润滑脂或自动传动液的添加剂，这些润滑油、润滑脂或自动传动液从含有较大量的粘性润滑油和较少量的添加剂的反应物制得，该添加剂从含有下述组份的反应物制得：
（A）二硫化碳、氧硫化碳或产生它们的原料，
（B）具有式R′R″NH的胺，其中R′和R″相同或不同，为1至大约7个碳原子的烷基、芳基或芳烷基，或二者一起形成脂环基或通过氮原子一起形成杂环基，
（C）具有下式的反应物：
其中，R10和R11独立地代表H、烷基、芳基、Cl或Br;R′为H、烷基、芳基或芳烷基;X为0或1，b为0或1（x+b为1）;R′ 3为H、烷基或芳基、氯或溴;Z为CN、
Figure 87101910_IMG21
、
Figure 87101910_IMG22
Figure 87101910_IMG23
（其中R5为H、烷基或芳烷基）、
Figure 87101910_IMG24
，其中Y为H、OH、R6（R6为烷基、芳基或芳烷基）、OR6、OR7-OH（R7为1至大约7个碳原子的亚烷基）、NR8R9（其中R8和R9独立地代表H、烷基、脂环基、杂环基或二者一起形成脂环基或通过氮原子一起形成杂环基，但X须为0，Y不能为OR6）。
16、一种含有权利要求11、13或15所述的添加剂的润滑脂组合物。
17、一种含有权利要求11、13或15所述的添加剂的自动传动液。
18、一种含有权利要求11、13或15所述的添加剂的液压液。
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ZA871937B (en) 1987-11-25
JPS63502905A (ja) 1988-10-27
SG56993G (en) 1993-07-09
EP0261177B1 (en) 1992-09-16
WO1987005622A1 (en) 1987-09-24
IN167202B (zh) 1990-09-22
DE3781755T2 (de) 1993-03-25
CA1288759C (en) 1991-09-10
CN1009560B (zh) 1990-09-12
CN1047691A (zh) 1990-12-12
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DE3781755D1 (de) 1992-10-22
EP0261177A1 (en) 1988-03-30

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